Derivatives of sulphonated amines and process of preparing same



Patented May 29, 1945 DERIVATIVES OF SULPHONA'IED AMINES AND PROCESS OF PREPARING SAME Charles Graenacher, Riehen, and Paul Streuli and Jules Meyer, Basel, Switzerland, assignors to the Swiss Company of Society of Chemical Industry in Basie, Basel, Switzerland Nd'Drawing. Application October 22, 1942, Serial No. 462,988. In Switzerland December 24, 194i 2 Claims.

It has been found that new derivatives of sulphonated amines are obtained if one mol of a sulphonated amine be condensed with at least one mol of an aralkylating agent containing at least 8 carbon atoms and, if desired, alkylating or acylating'agents be allowed to react upon the reaction products thus obtained, or if one moi of an amine be condensed with at least one mol of an aralkylating agent containing at least 8 carbon atoms and if sulphuric acid radicals are introduced into the reaction product-if desired, before or after the action of alkylating or acylating agents-by treatment with sulphonating agents.

By the term sulphonated amines, both aminosulphonic acids and sulphuric acid esters of hydroxyamines are to be understood.

As aminosulphonic acids, use may be made for example, of those of the aliphatic series, such as taurine, methylaminoethane sulphonic acid, but preferably of aromatic aminosulphonic acids, for instance, aminosulphonic acids of the benzene and naphthalene series, among which mention may be made of sulphanilic acid, N-monoethylsulphanilic acid, metanilic acid, l-aminobenzene-disulphonic acid-(2:4), halogenated aniline sulphonlc acids, sulphonic acids of toluidine and xylidine, 1:2-diaminobenzene sulphonic acid-(4), aminocymol sulphonic acids, monoamino-monosulphonic acids and monoamino-disulphonic acids of the naphthalene series, such as naphthionic acid, 1:6-naphthylamino-sulphonic acid, 2 G-naphthylamino-sulphonic acid, 2 :6 B-naphthylamine-disulphonic acid, moreover 2:3:6:8- naphthylamine-trisulphonic acid, l-aminotetrahydronaphthalene-4-sulphonic acid, l-amino-tetrahydronaphthalene-2:4-disulphonic acid, aminosulphonic acids of diphenyl, sulphonic acids of benzidine and dianisidine, aminosulphonic acids of anthracene, phenanthrene and acenaphthene,

etc. The aminosulphonic acids of the benzene and naphthalene series are hereinafter designated as aromatic amino-sulphonic acids containing at most two condensed benzene nuclei. In addition to the halogen atoms already mentioned, the aminosulphonic acids may also contain further substituents, such as hydroxyl groups.

As aminosulphonic acids, sulphonated aryl hydrazines, for example, phenylhydrazine para-sulphonic acid, 2-hydrazino-naphthalene disulphonic acid-(6:8), also come into consideration.

As examples of heterocyclic aminosulphonic acids, mention may be'made of carbazole sulphonic acids.

The amino group of the aminosulphonic acids can thus be primary or secondary in nature. Aminosulphonic acids with a secondary amino group, e. g. an amino group containing an alkyl radical, are suitable parent materials in many cases.

As an example of a sulphuric acid ester of a hydroxyamine, mention may be made of ethanolamine sulphuric acid ester.

As araikylating agents which contain at least 8 carbon atoms, chloromethyl compounds of aromatic or partially hydrogenated aromatic compounds are particularly suitable, for example, chloromethyi toluene, chloromethyl xylene, chloromethyl cumene, 2-chloromethyl cymene (cymyl chloride), l-chloromethyl naphthalene, chloromethyltetrahydronaphthalenes (for example, ar-2- chloromethyltetrahydronaphthalene identical with 6 chloromethylnaphthalene-1z2:3z4-tetrahydride), chloromethylcyclohexyl-benzene (obtained, for example, by treatment of the addition product of benzene and cyclohexene with formaldehyde, aqueous hydrochloric acid and hydro-' gen chloride gas at 60-70" C.) chloromethyl compounds of higher condensed aromatic ring systems and of their partially hydrogenated derivatives, for example, chloromethyl anthracene, chloromethyloctahydroanthracene, chloromethyloctahydrophenanthrene. Chloromethyltoluene, chloromethylxylene, chloromethylcumene and chloromethylcymene are examples of benzyl chlorides which are alkylated in the nucleus.

The chloromethyl derivatives of aromatic and partially hydrogenated aromatic hydrocarbons which are not as yet described in the literature can be prepared without trouble by analogous processes, for example, by the introduction of hydrogen chloride gas into a mixture of the hydrocarbon, concentrated formaldehyde and con centrated aqueous hydrochloric acidifdesired, with an addition of zinc chloride-heated to about 60-'70 C.

The reaction of the sulphonated amines, for example, of the aminosulphonic acids, with the aralkylating agents preferably takes place at raised temperature, if desired, in the presence of acid-binding agents, such as'sodium carbonate or calcium carbonate. For example, it is possible to react the aralkyl chlorides with aqueous solutions of the neutralized aminosulphonic acids at 6% C., an alkaline reaction of the solution being maintained by addition of sodium carbonate. When reacting p-aminoethane sulphonic acid, it is advisable to work in the presence of mixtures consisting 01. water and organic, water-soluble solvents, for example, with an addition of aqueous methanol to the reaction mixture.

It the reaction products obtained from the sulphonated amines and the aralkylating agents mentioned contain a secondary amino group, this may be further substituted in the usual manner by the action 01' alkylating agents, such as ethylene oxide, glycide, epichlorohydrine, or of acylating agents, such as acetic anhydride, butyric acid chloride, caproic acid chloride, lauric acid chloride, stearic acid chloride. In such cases, should more than 1 mol of a izz-alkylene-oxide be used per secondary amino group, polyslycol ether radicals can be introduced.

One method of carrying out the present process consists of reacting the aralykylating agents containing at least 8 carbon atoms with the corresponding unsulphonated amineainstead of with the sulphonated amines this maybe carried out in a manner similar to that already given for the aminosulphonic acids. The sulphuric acid radicals, i. e., sulphonic acid groups or sulphuric acid ester groups, are then introduced into the reaction products thus obtained by treatment with sulphonating agents, such as concentrated sulphuric acid, chlcrsulphonic acid, sulphuric acid containing sulphur trioxide. In this method, also, alkylating agents or-should secondary amino groups be present-acylatins agents can be caused to react either before or after the sulphonation.

The products of the present invention may be designated in the neutralized state as salts of sulphonated amines which are substituted in at least one amino group by at least 8 carbon atoms, which V The reaction with z-chlormethyl-cymene yields products which are substituted in at least one amino group by at least one cymylmethyl radical of the formula v a OHr- I 5 on cm 7 By reason of their capillary activity, the products of the present process can be used as textile auxiliary products, for example, as wetting, dispersing, washing, softening, levelling, or foaming agents. Products containing nuclear alhlated benzyl radicals, particularly those containing 1 or screen v which is characterized by an especially good washingcapacityandahighresistancetowardshardwatenthis resistance being better than the resistance of the corresponding derivatives of monoamino-rnonosulphonicacids of the naphthalene series.

The products of the present invention can be i Example 1 195 parts of sodium sulphanilate are dissolved in 650 parts by volume of water; 85 parts of sodium carbonate in 250 parts of water are added, and then, whilst stirring at IO-75 (3., 180 parts of ar-2-chloromethyl-tetrahydronaphthalene are introduced over a period of 3 hours. After stirring for a further period of several hours at IO-80 6., a clear solution is obtained, which should still have an alkaline reaction. This is neutralired and then evaporated to dryness.

The aralkylation product can also be separated from the mother liquor by acidifying with mineral acid or by salting out with common salt and cooling; in this way a yield of 810-320 parts of a salt-free product can be obtained.

The dry reaction product thus obtained, which possesses the formula moieONn-on Example 2 18.! parts of N-methylsulphanilic acid are neutralized with a 10 per cent. solution of sodium carbonate. Then, whilst stirring at -70" 0., 18.2 parts of 2+chloromsthyl cymene (prepared, for example,;from cymene, formaldehyde, and hydrochloric acid), together with rather more than the equivalent quantity of a sodium carbonate solution of 20 per cent. strength, are allowed to run inoveraperi0dof%hour,andthemixtureis SWIM a clear solution is obtained. This requiresaboutihmiraandcaremustbetaken that the solution always an alkaline reaction. hfterstin-ingforafurtherihoursat 65-70? C. the solution is neutralized and evaporated to dryness. The dry residue represents a yield of 39 parts.

The N-methyl-N-cymylmethylsulphanilic acid sodium salt thus obtained which corresponds to the formula 2 radicals introduced by means of chloromethyl cymene, form excellent wetting agents. .These cymylmethyl derivatives possess a much higher wetting capacity than corresponding products which contain naphthylmethyl or tetrahydronaphthylmethyl radicals instead of cymylmethyl radicals. Products containing tetrahydronaphthylmethyl radicals are remarkable for their washing action. Monoamino disulphonic acids of the naphthalene series which are substituted in the amino group by one or two tetrahydronaphthylmethyl radicals form a class of compounds CH C CHI is a colorless powder readily soluble in water. Its

solutions possess a high degree of wetting power Similar properties are possessed by N-cymylmethylmetanilic acid sodium salt, prepared in an analogous manner.

Example 3 180 parts of ar-2-chloromethyltetrahydronaphthalene (1 mol) are introduced over a period of 2-3 hours into a solution of 245 parts of 1:6- naphthylamine sulphonic acid sodium salt in 800 parts of water at "IO-75 C., the reaction mixture being stirred continuously. At the same time, suflicient sodium carbonate is added to maintain the reaction mass in a weakly alkaline state. When all the chloromethyltetrahydronaphthalene has been added, the reaction mixture is stirred at 70-80 C. until no more alkali is absorbed; hereupon, the reaction mixture in which much aralkylation product has precipitated, is neutralized and evaporated.

The product of the formula n NHCH:

NaOaS H thus obtained is a faint grey-violet colored powder yielding a clear solution in water.

Instead of the sodium salt of 1:6-naphthylamine-sulphonic acid the ammonium salt or an alkylolamine salt of naphthionic acid may be used in a similar manner.

Example 4 180 parts of ar-2-chloromethyltetrahydronaphthalene (1 mol) are introduced over a period of 2 hours whilst stirring into a solution of 347 parts of the disodium salt of 2:6: 8-naphthyl-' NBOBS H n H NH-CH n H N s is a yellowish powder yielding a clear solution with'a faint greenish fluorescence in water and possesses good foaming and washing properties.

Example 48.5 parts of acid potassium 2:6:8-naphthylamine disulphonate (containing 62.4 per cent. of disulphonic acid) are neutralized with a solution of sodium carbonate of per cent. strength, and. whilst stirring at 65-70 C., 36.4 parts of 2-chloromethyl cymene, together with rather more than the equivalent quantity of a 20 per cent. solution of sodium carbonate, are allowed to run in over a period of 3-4 hours. The mixture is stirred for a. further 4 hours, when it becomes clear. It is then neutralized and evaporated to dryness.

The yield 01 the dry residue amounts to 81.7 parts.

The sodium salt of 2-di(cymylmethyl)aminonaphthalene-6:8-disulphonic acid thus obtained, of the formula NaOuB (IIHI -NCH:

NBOIE CHr- H-CHI CH:- H-CH:

is a colorless powder, readily soluble in water. It possesses strong wetting and foaming properties and excellent washing power in a neutral bath.

If the quantity of cymyl chloride used in the above preparation be reduced by one-half, sodium N-mono cymylmethylnaphthylamine disul" phonate is obtained which also possesses good wetting and washing properties.

Example 6 Whilst stirring at 70-75 C., 360 parts of ar-2- chloro-methyl-tetrahydronaphthalene (2 mols.) are introduced into a solution of 347 parts of the disodium salt of 2:6:8-naphthylamine disulphonic acid in 500 parts by volume of water over a period of 4 hours, and simultaneously sufiicient sodium carbonate is added to maintain the reaction mixture always in an alkaline state. When all the chloromethyltetrahydronaphthalene has been introduced, stirring is continued at 70-80 C. until no more alkali is absorbed and a product which yields a clear solution in water has been obtained. The solution is then neutralised and evaporated to dryness.

The aralkylation product thus obtained, of the formula NaOaS H H H NCH in NaOzB H is a yellowish powder which dissolves in water with a green fluorescence. It possesses strong foaming capabilities and washing power to a high degree.

Instead of the disodium salt of 2:6:8-naphthylamine-disulphonic acid the dipotassium salt of 1:3:G-naphthylamine-disulphonic acid or salts of aminosulphonic acids of the anthracene series may be used in a similar manner.

Example 7 26.2 parts of technical sodium phenylhydrazine sulphonate (containing 68 per cent. of phenylhydrazine sulphonic acid) are neutralized with a sodium carbonate solution of 10 per cent.

strength. Whilst stirring at 65-70 C., 18.2 parts of 2-chlorometbyl cymene, together with rather more than the equivalent quantity of a solution of sodium carbonate of 20 per cent. strength, are allowed to run in over a period of hour. The mixture is then stirred for a further 5 hours, when a sample of the solution, after dilution. with water, yields a clear solution. The reaction mixture is then neutralized and evaporated to dry- Example 8 26.2 parts of technical phenylhydrazine sulphonie acid sodium salt (containing 68 per cent. of phenylhydrazine sulphonic acid) are neutralized with a-10 per cent. solution of sodium carbonate and. whilst stirring at 65-70 C., 36.4 parts of z-chloromethyl-cymene, together with rather more than the equivalent quantity of a 20 per cent. solution of sodium carbonate, are allowed to flow into the reaction mixture over a period of 3 hours. The mixture is then stirred for about 10 hours at the same temperature, when a sample'of the reaction liquor gives a clear solution on diluting it with water. The solution is then neutralized and evaporated to dryness.

The yield of dry substance amounts to 68.2 parts.

The N-di(cymylmethyl) -phenylhydrazine sulphonic acid sodium salt thus obtained is a colorless powder, not very readily soluble in water. of high wetting powers and good washing properties in a neutral bath.

trample 9 339 parts of the products obtained in Example 1 are heated for 10 hours at 150-160" C, in an autoclave with 88 parts of ethylene oxide (2 mols). 425-42! parts of the alkylation product or the probable formula ill! I!!! are obtained. This is a brown, resin-like, sticky mass which is soluble in water to a clear solution aind possesses good roaming and washing propert es.

The product obtained in Example 1 can also be alkylated with ethylene oxide in aqueous solution in the following manner. For example, the aqueous solution of the product obtained in Example 1 to which 1 mol. of ethylene oxide has been added is heated in an autoclave for 5 hours at 110-l20 C. The ethylene oxide is fully absorbed during this time. and an alkylation product is obtained which is very similar to the one described above.

Example 10 34 parts of the product obtained in Example 1 are suspended in 50 parts of dry Pyridine and. whilst stirring at 50 (7., 20 parts of lauric acid chloride are slowly introduced. the reaction mix- I ture gradually becoming warmer. When all has been added, the reaction mixture is stirred for 30 minutes at 80-90 0., after which it is left to cool; it is then poured into water and acidified with sulphuric acid, when the .precipitated acylation product is filtered oil at the pump. This latter is then suspended in water. neutralized with sodium carbonate and the resultant clear solution is evaporated to dryness.

The new product of the formula is a. pale brown powder which dissolves to a clear solution in water and possesses very good wetting, washing and foaming properties.

Example 11 18 parts of p-aminoethane sulphonic acid sodium salt, together with 10 parts of water, 30 parts of methyl alcohol, and 48 parts of 2-chloromethyl-cymene (cymyl chloride) are boiled under reflux, the weak alkalinity of the reaction mixture being maintained by addition of caustic soda solution.

The reaction is completed after some hours, and the reaction mixture is then neutralized with mineral acid and evaporated to dryness under reduced pressure. By extracting the dry residue with absolute alcohol the product can be obtained in a salt-free state. I

The p-di(cymylmethyl) amino-ethane sulphonic acid sodium salt of the formula CHI /CH NICE-CHg-C 8 -11 is a hygroscopic powder not very readily soluble in water and possesses excellent wetting powers.

If only half the quantity of cymyl chloride be used in the above preparation, p-monocymylmethylaminoethane-sulphonic acid sodium salt is obtained, the aqueous solutions of which have also excellent wetting properties.

Dioxane can be usedin the above preparation in place of methyl alcohol.

Instead of the sodium salt of p-amino-ethanesuiphonic acid the sodium salt or p-methylamineethane-sulphonic acid or of the acid sulphuric acid ester or ethanolamine may be used in a similar manner.

Example 12 iormula mom-oaP-cm -Nn-e is a hygroscopic powder not very readily soluble in water. It possesses good capillary active properties, especially good wetting properties.

If double the amount of ar-2-chloromethyltetrahydronaphthalene be used in the above preparation, the sodium salt of p-di-tetrahydronaphtlwlmethylaminoethane sulphonic acid is obtained; this also possesses good wetting powers.

Example 13 For the washing of 50 kg. of wool yarn, a bath is prepared which contains 0.3 to 0.6 gm. of the product obtained in Example 6 per liter of water at 45 C. The ratio of material to liquor is 1:20. The wool is entered and worked for hour, after which it is rinsed. After this treatment the material is excellently scoured and can be dyed without further preparation.

Example 14 In order to wet-out cotton or woolen yarns, a bath is used containing per liter 0.5 gram of the product prepared in mample 8 plus 1.5 grams sodium sulphate. The material is very rapidly wetted by this liquor.

What we claim is:

4 nos n n 0 nos H on n 1. The salts of the sulphonic acid of the formula H /Ri I I I wherein R1 stands for the same member of the 10 group consisting of the radical and the radical, which salts are. solid to liquid substances soluble in water to form stable capillary active solutions.

2. The salts of the sulphonic acid oi the formula which salts are solid to liquid substances soluble in water to form stable capillary active solutions of a good washing power.

CHARLES GRAENACHER.

PAUL STREULI.

JULIE MEYER. 

